CN108706564A - A kind of preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate - Google Patents
A kind of preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of preparation methods of high-pressure solid lithium ion battery anode material lithium iron phosphate, include the following steps：S1, by compound source of iron, phosphorus source and the carbon source dispensing by a certain percentage of lithium source, ferric orthophosphate and metal iron powder composition, it puts into Scattered Kettle, solvent is added and disperseed, roughly ground and fine grinding, uniformly mixed slurry is obtained, slurry is spray-dried, spherical precursor powder is obtained；S2, gained precursor powder is carried out to tabletting granulation densification, obtains granular presoma；S3, by the granular presoma of gained, high temperature sintering under inert gas protection, then cooled to room temperature, then be grinding to obtain high-pressure solid LiFePO4 product.The present invention uses compound source of iron, and the density of metal iron powder is higher, a nanometer level ferric orthophosphate, the LiFePO4 of synthesis is coordinated to have excellent chemical property and higher tap density again；Tabletting is carried out to spray drying gained precursor powder and is granulated densification, improves sintering production efficiency and LiFePO 4 material density.
Description
Technical field
The present invention relates to lithium ion battery material technical field more particularly to a kind of high-pressure solid anode material for lithium-ion batteries
The preparation method of LiFePO4.
Background technology
New-energy automobile newly subsidizes scheme using battery system energy density as subsidy standard, especially the benefit of integral new-energy passenger
Patch is differed greatly by the performance rate of power battery.Although the LiFePO4 single battery core energy density of many battery enterprises at present
Can accomplish 140wh/kg or so, but in groups after battery system energy density be no more than 120wh/kg mostly.This means that
Most of most of vehicle declared can only obtain deep low gear subsidy standard, to serious blow vehicle enterprise development pure electric coach
Enthusiasm.This requires the LiFePO 4 material of positive electrode Corporation R & D higher performance.
Compacted density is the ratio between the thickness of battery pole piece material coating surface density and material after pole piece compacting.Lithium ion power
In the production process, compacted density has large effect to battery to battery performance.In general, compacted density is bigger, same specification
The capacity of size battery can be done higher, so compacted density is also seen as one of the reference index of material energy densities.It can
To think, under conditions of battery specifications model is fixed, process conditions are certain, compacted density is bigger, and the capacity of single battery is got over
The unit overall cost of height, battery is also lower.But the compacted density of general LiFePO 4 material is relatively low, is only capable of reaching 2.3~
2.35g/cm3Left and right.If the compacted density of LiFePO 4 material can be increased substantially, the ratio energy of ferric phosphate lithium cell can
To increase substantially.
Application No. is the Chinese patent applications of CN106744780A to disclose a kind of high-pressure solid anode material for lithium-ion batteries
The preparation method of LiFePO4, this method include：(1) lithium source, high-pressure solid source of iron, phosphorus source and solvent are first mixed, adds and mixes
Miscellaneous metal oxide, dispersant continue to mix, and are eventually adding carbon source mixing, uniformly mixed slurry, which is dispersed through, to be dried solid
Body powder particle；(2) solid powder particle is subjected to air-flow crushing；(3) it is equipped with inert gas shielding by what comminuting matter was put
It is heat-treated in rotary furnace, after material natural cooling, is transferred in the high temperature sintering furnace equipped with inert gas shielding and carries out height
Warm processing obtains the LiFePO4 of high compacted density then by natural cooling, sieving and air current classifying.Application invention
Secretary carries：This method proposes compacted density that is a kind of simple for process and can significantly improving lithium iron phosphate positive material, but the party
The phosphorus source that method uses will produce a large amount of ammonias in the synthesis process for ammonium salt-containing class, need to put into a large amount of exhaust-gas treatment cost
And pollute the environment, the LiFePO4 in addition prepared from iron oxide and ferroso-ferric oxide for source of iron, material electrical property is bad.
Invention content
The aimed to solve the problem that above-mentioned technical problem of the present invention, provide it is a kind of it is simple for process, be suitble to industrialized production, environmentally friendly height
The method for preparing lithium iron phosphate material of compacting and function admirable.The present invention adopts the following technical scheme that：
A kind of preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate, includes the following steps：
S1, compound source of iron, phosphorus source and carbon source that lithium source, ferric orthophosphate and metal iron powder form are matched according to a certain percentage
Then material is put into Scattered Kettle, solvent is added and disperseed as dispersant, roughly ground and fine grinding, uniformly mixed slurry is obtained,
Slurry is spray-dried, spherical precursor powder is obtained；
S2, gained precursor powder is carried out to tabletting granulation densification, i.e., it will spray drying gained spherical precursor powder
It is broken, obtain granular presoma；
S3, by the granular presoma of gained, high temperature sintering under inert gas protection, then cooled to room temperature, then pass through
Crush to obtain high-pressure solid LiFePO4 product.
The compound source of iron that the present invention is formed using ferric orthophosphate and metal iron powder, metal iron powder have higher density, use
The LiFePO4 that it is synthesized has higher tap density compared with other raw material, improves LiFePO 4 material density, collocation
Ferric orthophosphate can obtain excellent chemical property；Tabletting is carried out to precursor powder and is granulated densification, improves material sintering
Mass transfer in the process and rate of heat transfer, processing performance is excellent, and compacted density is high；Slurry grinding include roughly grind, two steps of fine grinding,
Grinding efficiency is improved, slurry mixing is more uniform, and slurry granularity is small and easy to control, is conducive to obtain high-pressure solid product.
Further, the compound source of iron uses the mixture of micro-sized metal iron powder and nanometer level ferric orthophosphate；Not only
With excellent chemical property, while the metal iron powder of size particles and ferric orthophosphate grading, phosphoric acid can be further increased
Iron lithium material density；
Preferably, the compound source of iron is the D50=1~2um metal iron powders prepared using reduction method, is with primary particle
The mixture of the ferric orthophosphate of 50~200nm.
Further, Li in dispensing described in step S1：Fe：The molar ratio of P is (0.9~1.2)：1：(0.8~1.0),
It is 3~15% that carbon source, which accounts for the weight ratio in mixture,；
Further, the mixing molar ratio of metal iron powder and ferric orthophosphate is 1 in the compound source of iron：1~1：10, this
The LiFePO 4 material density obtained within the scope of grain composition is big, it is preferable that the mixing molar ratio is 1：2~1：5.
Further, further include at least one following technical characteristic in step S1：
The lithium source includes lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium citrate, lithium acetate
In any one or two or more mixtures；
Phosphorus source includes any one or two or more mixtures in ferric phosphate, lithium dihydrogen phosphate, phosphoric acid；
The carbon source using glucose, polyvinyl alcohol, sucrose, PVP, polyethylene glycol, phenolic resin, hexamethylenetetramine,
It is one or more in citric acid；
The solvent uses ethyl alcohol, isopropanol, acetone or deionized water.
Further, in step S1, the addition of solvent is the 20%~60% of slurry solid content, jitter time is 1~
3h；
Further, in step S1, the corase grinding time is 1~5h, and slurry granularity D50 controls are in 1~2um after corase grinding；
Further, in step S1, the fine grinding time is 2~6h, and slurry granularity D50 controls are in 400~800nm after fine grinding.
Further, be spray-dried described in step S1, inlet air temperature be 200 DEG C~300 DEG C, leaving air temp be 50 DEG C~
100℃。
Further, it is 10~100MPa that tabletting described in step S2, which is granulated pressure used,；
Further, the temperature of step S3 high temperatures sintering is 700 DEG C~800 DEG C, and sintering time is 6~12h.
Further, inert atmosphere described in step S3 is one or more in nitrogen, helium, neon, argon gas, is passed through
Air-flow crushing or mechanical crushing obtain high-pressure solid LiFePO4 product.
Further, gained high-pressure solid LiFePO4 product granularity D50 controls exist in 2~5um, D90 controls in step S3
≤ 12um, product granularity composition is reasonable, and is matched by size granularity grade, realizes the filling of hole, improves LiFePO4 material
The compacted density of material；In 1.4 ± 0.5wt%, carbon content can influence the specific surface area of LiFePO 4 material and lead carbon content control
Electrically, carbon content is excessively high, and the specific surface area of material increases, and particle is easy to coalesce together, and carbon content is too low, then the conduction of material
Performance is poor.
What the present invention obtained has the beneficial effect that：
(1) present invention uses D50=1~2um metal iron powders (purity >=98.5%), is 50~200nm with primary particle
Ferric orthophosphate use the compound source of iron of composition in proportion, metal iron powder has higher density, with the LiFePO4 of its synthesis with
Other raw material are compared, and have higher tap density, then coordinate a nanometer level ferric orthophosphate, not only have excellent electrochemistry
Can, simultaneously because size particles grading, can further increase LiFePO 4 material density；
(2) present invention carries out tabletting to precursor powder and is granulated densification, and spray drying gained hollow ball-shape powder is broken
It is broken, it obtains granular presoma, solves the poor processability that hollow ball is brought, the problems such as compacted density is low；Improve material sintering process
In mass transfer and rate of heat transfer, material is uniform between batch, and processing performance is excellent；Solution powder density is small, and sintering production efficiency is low
The problem of；
(3) present invention includes two corase grinding, fine grinding steps to slurry grinding, improves grinding efficiency, and slurry mixes more
Uniformly, slurry granularity is small and easy to control, is conducive to obtain high-pressure solid product；
(4) product granularity composition of the present invention is reasonable, and is matched by size granularity grade, realizes the filling of hole, improves
The compacted density of LiFePO 4 material；Carbon content control has taken into account the electric conductivity and specific surface of material in 1.4 ± 0.5wt%
Product；
(5) invention provide method flow is short, environmental protection simple for process, reaction condition is mild, suitable for applying to industrial metaplasia
Production.
Description of the drawings
Fig. 1 is the method flow schematic diagram of the present invention；
Fig. 2 is the SEM figures of iron phosphate powder prepared by embodiment 1；
Fig. 3 is the SEM figures of iron phosphate powder prepared by embodiment 2；
Fig. 4 is the SEM figures of iron phosphate powder prepared by embodiment 3；
Fig. 5 is the SEM figures of iron phosphate powder prepared by embodiment 4；
Fig. 6 is the SEM figures of iron phosphate powder prepared by embodiment 5；
Fig. 7 is the SEM figures of iron phosphate powder prepared by comparative example 1；
Fig. 8 is the SEM figures of iron phosphate powder prepared by comparative example 2；
Fig. 9 is the SEM figures of iron phosphate powder prepared by comparative example 3.
Specific implementation mode
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear
Chu is fully described by, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts all
Other embodiment shall fall within the protection scope of the present invention.
Embodiment 1：
By lithium carbonate (Li2CO3) 63.36 kilograms, the ferric orthophosphate (FePO that primary particle is 50~200nm4) 250.00 thousand
Gram, lithium dihydrogen phosphate (LiH2PO4) 18.79 kilograms, 10.24 kilograms of D50=2um metal iron powders, 19.00 kilograms of glucose, poly- second
11.00 kilograms of glycol is placed in Scattered Kettle, and then addition deionized water 630L is disperseed, slurry jitter time is 1h, then
Roughly ground, the corase grinding time is 3h, after corase grinding slurry granularity D50 controls finally carry out fine grinding in 1~2um, the fine grinding time is
4h, slurry granularity D50 is controlled in 500nm after fine grinding, obtains homogeneous mixed slurry.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 240 DEG C, is gone out
Air temperature is controlled at 90 DEG C, obtains spherical precursor powder；Then precursor powder is subjected to tabletting and is granulated densification, tabletting is made
Pressure used in grain is 70MPa, obtains granular presoma.
Granular presoma is placed in the kiln with protective atmosphere nitrogen and is sintered, sintering temperature is 770 DEG C, is burnt
It is 8 hours to tie the time, and cooled to room temperature is grinding to obtain high-pressure solid iron phosphate powder, and the compacted density of product is
2.80g/cm3.The SEM microscopic appearances of product are shown in Fig. 2, and material surface rounding is smooth, and carbon coating is uniform, and particle diameter distribution is uniform, has
Conducive to the properties for follow of raising material.
Embodiment 2：
By lithium carbonate (Li2CO3) 50.69 kilograms, the ferric orthophosphate (FePO that primary particle is 50~100nm4) 200.00 thousand
Gram, lithium dihydrogen phosphate (LiH2PO4) 57.96 kilograms, 31.59 kilograms of D50=1um metal iron powders (purity >=98.5%), glucose
18.5 kilograms, 9.50 kilograms of water soluble phenol resin be placed in Scattered Kettle, then be added deionized water 550L disperseed, slurry
Jitter time is 2h, is then roughly ground, and the corase grinding time is 1h, and slurry granularity D50 controls are most laggard in 1~1.5um after corase grinding
Row fine grinding, fine grinding time are 6h, and slurry granularity D50 is controlled in 400nm after fine grinding, obtains homogeneous mixed slurry.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 280 DEG C, is gone out
Air temperature control obtains spherical precursor powder at 100 DEG C；Then precursor powder is subjected to tabletting and is granulated densification, tabletting is made
Pressure used in grain is 50MPa, obtains granular presoma.
Granular presoma is placed in the kiln with protective atmosphere argon gas and is sintered, sintering temperature is 750 DEG C, is burnt
It is 10 hours to tie the time, cooled to room temperature, is grinding to obtain high-pressure solid iron phosphate powder, and product granularity D50 controls exist
3um, D90 are controlled in 10um.The compacted density of products obtained therefrom is 2.95g/cm3.The SEM microscopic appearances of product are shown in Fig. 3, material table
Face rounding is smooth, and carbon coating is uniform, and particle diameter distribution is uniform, is conducive to the properties for follow for improving material.
Embodiment 3：
By lithium carbonate (Li2CO3) 38.02 kilograms, the ferric orthophosphate (FePO that primary particle is 50~150nm4) 150.00 thousand
Gram, lithium dihydrogen phosphate (LiH2PO4) 101.44 kilograms, 55.30 kilograms of D50=1.5um metal iron powders (purity >=98.5%), sugarcane
19.00 kilograms of sugar, 5.00 kilograms of polyvinyl alcohol, 6.00 kilograms of PVP are placed in Scattered Kettle, and ethyl alcohol 520L is then added and is divided
Dissipate, slurry jitter time is 2h, is then roughly ground, the corase grinding time is 3h, after corase grinding slurry granularity D50 control 1.2~
2um finally carries out fine grinding, and the fine grinding time is 5h, and slurry granularity D50 is controlled in 600nm after fine grinding, obtains homogeneous mixed slurry.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 220 DEG C, is gone out
Air temperature control obtains spherical precursor powder at 70 DEG C；Then precursor powder is subjected to tabletting and is granulated densification, tabletting is made
Pressure used in grain is 80MPa, obtains granular presoma.
Granular presoma is placed in the kiln with protective atmosphere neon and is sintered, sintering temperature is 720 DEG C, is burnt
It is 12 hours to tie the time, cooled to room temperature, and high-pressure solid iron phosphate powder, product granularity D50 controls are obtained through air-flow crushing
System is controlled in 2um, D90 in 12um.The compacted density of products obtained therefrom is 2.84g/cm3.The SEM microscopic appearances of product are shown in Fig. 4, material
Expect that surface rounding is smooth, carbon coating is uniform, and particle diameter distribution is uniform, is conducive to the properties for follow for improving material.
Embodiment 4：
By lithium acetate (CH3COOLi) 121.42 kilograms, the ferric orthophosphate (FePO that primary particle is 100~200nm4)
230.00 kilograms, 17.10 kilograms of D50=1um metal iron powders, 25.00 kilograms of polyethylene glycol, 5.00 kilograms of hexamethylenetetramine,
12.00 kilograms of citric acid is placed in Scattered Kettle, and then addition isopropanol 500L is disperseed, slurry jitter time is 3h, then
Roughly ground, the corase grinding time is 4h, after corase grinding slurry granularity D50 controls finally carry out fine grinding in 1um, the fine grinding time is 3h, carefully
Slurry granularity D50 controls obtain homogeneous mixed slurry in 700nm after mill.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 200 DEG C, is gone out
Air temperature control obtains spherical precursor powder at 60 DEG C；Then precursor powder is subjected to tabletting and is granulated densification, tabletting is made
Pressure used in grain is 30MPa, obtains granular presoma.
Granular presoma is placed in the kiln with protective atmosphere helium and is sintered, sintering temperature is 800 DEG C, is burnt
It is 6 hours to tie the time, cooled to room temperature, and high-pressure solid iron phosphate powder, product granularity D50 controls are obtained through mechanical crushing
It is controlled in 8um in 3um, D90.The compacted density of products obtained therefrom is 2.86g/cm3.The SEM microscopic appearances of product are shown in Fig. 5, material
Surface rounding is smooth, and carbon coating is uniform, and particle diameter distribution is uniform, is conducive to the properties for follow for improving material.
Embodiment 5：
By 65.70 kilograms of lithium hydroxide (LiOH), lithium nitrate (LiNO3) 72.54 kilograms, primary particle be 100~150nm
Ferric orthophosphate (FePO4) 350.00 kilograms, phosphoric acid (H3PO4) 76.74 kilograms, D50=1.8um metal iron powders (purity >=
98.5%) 63.18 kilograms, 25.00 kilograms of polyvinyl alcohol, 10.00 kilograms of water soluble phenol resin be placed in Scattered Kettle, then plus
Enter that acetone 1100L is disperseed, slurry jitter time is 1h, is then roughly ground, the corase grinding time is 5h, slurry granularity after corase grinding
D50 is controlled in 2um, finally carries out fine grinding, and the fine grinding time is 2h, and slurry granularity D50 is controlled in 800nm after fine grinding, is obtained homogeneous
Mixed slurry.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 210 DEG C, is gone out
Air temperature control obtains spherical precursor powder at 55 DEG C；Then precursor powder is subjected to tabletting and is granulated densification, tabletting is made
Pressure used in grain is 100MPa, obtains granular presoma.
Granular presoma is placed in the kiln with protective atmosphere nitrogen and is sintered, sintering temperature is 760 DEG C, is burnt
It is 9 hours to tie the time, cooled to room temperature, and high-pressure solid iron phosphate powder, product granularity D50 controls are obtained through air-flow crushing
It is controlled in 12um in 5um, D90.The compacted density of products obtained therefrom is 2.91g/cm3.The SEM microscopic appearances of product are shown in Fig. 6, material
Surface rounding is smooth, and carbon coating is uniform, and particle diameter distribution is uniform, is conducive to the properties for follow for improving material.
Comparative example 1：
By lithium carbonate (Li2CO3) 63.36 kilograms, ferric orthophosphate (FePO4) 250.00 kilograms, it is 20.00 kilograms of glucose, poly-
7.50 kilograms of ethylene glycol is placed in Scattered Kettle, and deionized water 630L is then added and disperseed, roughly grind and fine grinding, slurry point
It is 1h to dissipate the time, and the corase grinding time is 3h, and in 1~2um, the fine grinding time is 4h, slurry after fine grinding for slurry granularity D50 controls after corase grinding
Granularity D50 controls obtain homogeneous mixed slurry in 500nm.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 240 DEG C, is gone out
Air temperature control obtains spherical precursor powder at 90 DEG C；Then precursor powder is subjected to tabletting and is granulated densification, tabletting is made
Pressure used in grain is 70MPa, obtains granular presoma.
Granular presoma is placed in the kiln with protective atmosphere nitrogen and is sintered, sintering temperature is 770 DEG C, is burnt
It is 8 hours to tie the time, and cooled to room temperature is grinding to obtain high-pressure solid iron phosphate powder, and the compacted density of product is
2.56g/cm3.The SEM microscopic appearances of product are shown in Fig. 7, and metal iron powder is added without in source of iron, and obtained material surface corner angle are more,
Particle diameter distribution is uneven, range is larger, and the properties for follow of material is general, and compacted density is relatively low.
Comparative example 2：
By lithium carbonate (Li2CO3) 63.36 kilograms, ferric orthophosphate (FePO4) 250.00 kilograms, it is 20.00 kilograms of glucose, poly-
7.50 kilograms of ethylene glycol is placed in Scattered Kettle, and deionized water 630L is then added and disperseed, roughly grind and fine grinding, slurry point
It is 1h to dissipate the time, and the corase grinding time is 3h, and in 1~2um, the fine grinding time is 4h, slurry after fine grinding for slurry granularity D50 controls after corase grinding
Granularity D50 controls obtain homogeneous mixed slurry in 500nm.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 240 DEG C, is gone out
Air temperature control obtains spherical precursor powder at 90 DEG C.
Spherical precursor is placed in the kiln with protective atmosphere nitrogen and is sintered, sintering temperature is 770 DEG C, is burnt
It is 8 hours to tie the time, cooled to room temperature, is grinding to obtain iron phosphate powder, the compacted density of product is 2.30g/
cm3.The SEM microscopic appearances of product are shown in Fig. 8, and metal iron powder is added without in source of iron and is granulated without tabletting, obtained material table
The coarse corner angle in face are more, and agglomeration is serious, and particle diameter distribution is uneven, range is larger, and the properties for follow of material is general, compacting
Density is low.
Comparative example 3：
By lithium carbonate (Li2CO3) 63.36 kilograms, ferric orthophosphate (FePO4) 250.00 kilograms, 2um metal iron powders 10.24 thousand
Gram, 20.00 kilograms of glucose, 7.50 kilograms of polyethylene glycol be placed in Scattered Kettle, then be added deionized water 630L carried out
Dispersion, corase grinding and fine grinding, slurry jitter time are 1h, and the corase grinding time is 3h, and slurry granularity D50 is controlled in 1~2um after corase grinding,
The fine grinding time is 4h, and slurry granularity D50 is controlled in 500nm after fine grinding, obtains homogeneous mixed slurry.
Then obtained uniformly mixed slurry is spray-dried, spray drying EAT is controlled at 240 DEG C, is gone out
Air temperature control obtains spherical precursor powder at 90 DEG C.
Spherical precursor is placed in the kiln with protective atmosphere nitrogen and is sintered, sintering temperature is 770 DEG C, is burnt
It is 8 hours to tie the time, cooled to room temperature, is grinding to obtain iron phosphate powder, the compacted density of product is 2.49g/
cm3.The SEM microscopic appearances of product are shown in Fig. 9, are granulated without tabletting in preparation process, obtained material surface is rougher, grain size
It is unevenly distributed, the properties for follow of material is general, and compacted density is relatively low.
By above example and the tap density of comparative example products obtained therefrom, compacted density, carbon content and chemical property into
Row comparison.
Wherein, electrochemical property test is：
Charge-discharge test, half-cell are carried out to the iron phosphate powder material prepared in Examples 1 to 5, comparative example 1~3
Test condition is as follows：
The test of battery carries out under room temperature (25 DEG C), and preparing for positive plate is as follows：With NMP (N-2- methyl pyrrolidones)
For solvent and dispersant, by the LiFePO 4 powder positive electrode of 80% (mass ratio) being prepared, 10% super P
Slurry is made in (super conductive black), 10% bonding agent (Kynoar, PVDF) mixing, and the solid content of slurry is 45%, so
Slurry is coated on the aluminium foil of 20 μ m-thicks afterwards and is made film, then by film through 120 DEG C of vacuum drying backlash at 10mm thin slices, system
At positive plate.In the glove box filled with high-purity argon gas, using metal lithium sheet as cathode, using 2400 films of Celgard (from market
The diaphragm of purchase) as diaphragm, electrolyte is the LiPF of 1mol/L6/ (EC+DME), assembling obtain simulated battery, carry out charge and discharge
Electrical testing.
Correction data such as table 1：
1. experimental data of table compares
From the data in the table, with the LiFePO 4 material of the method for the present invention preparation on the basis of ensureing capacitance,
Tap density and compacted density are significantly improved.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features,
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate, which is characterized in that include the following steps：
S1, by compound source of iron, phosphorus source and the carbon source dispensing according to a certain percentage of lithium source, ferric orthophosphate and metal iron powder composition,
Then it puts into Scattered Kettle, solvent is added and disperseed as dispersant, roughly ground and fine grinding, uniformly mixed slurry is obtained, general
Slurry is spray-dried, and spherical precursor powder is obtained；
S2, gained precursor powder is carried out to tabletting granulation densification, obtains granular presoma；
S3, by the granular presoma of gained, high temperature sintering under inert gas protection, then cooled to room temperature, then through crushing
Obtain high-pressure solid LiFePO4 product.
2. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as described in claim 1, which is characterized in that
The compound source of iron uses the mixture of micro-sized metal iron powder and nanometer level ferric orthophosphate；
Preferably, the compound source of iron is D50=1~2um metal iron powders, with the ferric orthophosphate that primary particle is 50~200nm
Mixture.
3. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as claimed in claim 2, which is characterized in that
Li in dispensing described in step S1：Fe：The molar ratio of P is (0.9~1.2)：1：(0.8~1.0), carbon source account for the weight in mixture
Amount is than being 3~15%.
4. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as claimed in claim 3, which is characterized in that
The mixing molar ratio of metal iron powder and ferric orthophosphate is 1 in the compound source of iron：1~1：10, it is preferable that the mixing mole
Ratio is 1：2~1：5.
5. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as claimed in claim 4, which is characterized in that
In step S1, the addition of solvent is the 20%~60% of slurry solid content, and jitter time is 1~3h；
The corase grinding time is 1~5h, and slurry granularity D50 controls are in 1~2um after corase grinding；
The fine grinding time is 2~6h, and slurry granularity D50 controls are in 400~800nm after fine grinding.
6. the preparation method of the high-pressure solid lithium ion battery anode material lithium iron phosphate as described in any one of claim 1 to 5,
Further include at least one following technical characteristic it is characterized in that, in step S1：
The lithium source includes in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium citrate, lithium acetate
Any one or two or more mixtures；
Phosphorus source includes any one or two or more mixtures in ferric phosphate, lithium dihydrogen phosphate, phosphoric acid；
The carbon source is using glucose, polyvinyl alcohol, sucrose, PVP, polyethylene glycol, phenolic resin, hexamethylenetetramine, lemon
It is one or more in acid；
The solvent uses ethyl alcohol, isopropanol, acetone or deionized water.
7. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as claimed in claim 6, which is characterized in that
It is spray-dried described in step S1, inlet air temperature is 200 DEG C~300 DEG C, and leaving air temp is 50 DEG C~100 DEG C.
8. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as claimed in claim 7, which is characterized in that
It is 10~100MPa that tabletting described in step S2, which is granulated pressure used,；The temperature of step S3 high temperatures sintering is 700 DEG C~800
DEG C, sintering time is 6~12 hours.
9. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as claimed in claim 8, which is characterized in that
Inert atmosphere described in step S3 is one or more in nitrogen, helium, neon, argon gas, passes through air-flow crushing or mechanical powder
It is broken to obtain high-pressure solid LiFePO4 product.
10. the preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate as claimed in claim 9, feature exist
In gained high-pressure solid LiFePO4 product granularity D50 controls are in 2~5um in step S3, and D90 controls are in≤12um, carbon content control
System is in 1.4 ± 0.5wt%.
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| CN109585809A (en) * | 2018-11-08 | 2019-04-05 | 山东精工电子科技有限公司 | A kind of shaggy LiFePO 4 material and preparation method thereof |
| CN109650366A (en) * | 2018-11-22 | 2019-04-19 | 湖北融通高科先进材料有限公司 | A kind of LiFePO4 and preparation method thereof |
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| CN110745802A (en) * | 2019-10-14 | 2020-02-04 | 重庆特瑞电池材料股份有限公司 | Method for preparing lithium iron phosphate by electromagnetic induction self-heating |
| CN112768688A (en) * | 2019-11-05 | 2021-05-07 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate material, preparation method thereof and lithium ion battery |
| CN112723333A (en) * | 2020-12-11 | 2021-04-30 | 江苏锂源电池材料有限公司 | Method for improving low-temperature performance and compaction density of lithium iron phosphate |
| CN114162800A (en) * | 2021-11-15 | 2022-03-11 | 广东派勒智能纳米科技股份有限公司 | Production method of lithium ion battery anode material |
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| CN114804058A (en) * | 2022-05-27 | 2022-07-29 | 湖北万润新能源科技股份有限公司 | High-tap-density lithium iron phosphate cathode material and preparation method and application thereof |
| CN115072694A (en) * | 2022-06-28 | 2022-09-20 | 衢州华友钴新材料有限公司 | Lithium iron phosphate anode material, preparation method thereof and lithium ion battery |
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